# Patent

## Title
Method and apparatus for prolonging the service life of a collective protection filter using a guard bed

## Abstract

A method for extending the service life of a Collective Protection (CP) filter includes: providing at least one CP filter comprising a filter bed; and passing an airstream through a guard bed configured to protect the filter bed by removing one or more of airborne contaminants and battlefield contaminants. An apparatus for extending the service life of a CP filter includes: a CP filter comprising a filter bed; and a guard bed configured to protect the filter bed by removing one or more of airborne contaminants and battlefield contaminants.

## Background
GOVERNMENT INTEREST
The invention described herein may be manufactured, used and/or licensed by or for the U.S. Government.


CROSS-REFERENCE TO RELATED APPLICATION
This application contains subject matter that is related to the subject matter of the following application, which is assigned to the same assignee as this application. The below-listed application is hereby incorporated herein by reference in its entirety:

    
    
        “METHOD AND APPARATUS FOR PROLONGING THE SERVICE LIFE OF A COLLECTIVE PROTECTION FILTER USING A SUPPLEMENTAL BED,” by Peterson, et al., co-filed herewith.
    
    


SUMMARY
According to embodiments of the invention, a method for extending the service life of a Collective Protection (CP) filter includes: providing at least one CP filter comprising a filter bed; and passing an airstream through a guard bed configured to protect the filter bed by removing one or more of airborne contaminants and battlefield contaminants.
According to other embodiments of the invention, an apparatus for extending the service life of a CP filter includes: a CP filter comprising a filter bed; and a guard bed configured to protect the filter bed by removing one or more of airborne contaminants and battlefield contaminants.



DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a Guard Bed located within an annular space upstream of the collective protection filter.
FIG. 2 is a flowchart of a method for extending the service life of a Collective Protection (CP) filter using a Guard Bed.



DETAILED DESCRIPTION
While the present invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail one or more specific embodiments, with the understanding that the present disclosure is to be considered as exemplary of the principles of the invention and not intended to limit the invention to the specific embodiments shown and described. In the following description and in the several figures of the drawings, like reference numerals are used to describe the same, similar or corresponding parts in the several views of the drawings.
Collective protection (CP) filters are designed to remove chemical warfare agents and toxic threat compounds from streams of air, thereby providing safe breathing to personnel in a chemically contaminated environment. In their simplest form, a CP filter is a device that allows air to flow through a gas filter bed of activated, impregnated carbon media in a manner that facilitates contact between the airstream and the carbon media. In addition, a particulate filter may be integrated into the CP filter upstream of the gas filter to remove aerosol and particulate matter. CP filters have a high initial capacity for removing chemical warfare agents and other toxic chemicals in the event of a chemical attack. However, such filters may have limited lifetime due to degradation resulting from one or more of exposure to airborne contaminants, exposure to battlefield contaminants, and the natural decay of the filtration media. The CP gas filter may, according to embodiments of the invention, be integrated with a High Efficiency Particulate Absorption (HEPA) filter.
CP filters are used by the US military in conjunction with naval vessels, vehicles, shelters, and buildings to provide breathable air to personnel in the event of a chemical attack. CP filters may be in operation on a continuous or near continuous basis, processing large volumes of air during their lifetime.
CP filters are employed in military and civilian settings. These large-scale filters or filter banks may provide breathable air and chemical protection to personnel located in buildings, ships, vehicles, and mobile tents, for example, during a chemical attack or chemical threat scenario employing chemical warfare agents and/or toxic threat compounds. Examples of chemical warfare agents and toxic threat compounds include hydrogen cyanide (HCN, also known as AC), chlorine gas (Cl2), phosgene (COCl2, also known as CG), cyanogen chloride (ClCN, also known as CK), mustard gas (bis(2-chloroethyl) sulfide, also known as HD), sarin ((RS)-Propan-2-yl methylphosphono-fluoridate, also known as GB) and O-ethyl S-[2-(diisopropylamino)ethyl]methylphosphonothioate (also known as VX).
Ambient air contains low levels of contaminants. Examples of these contaminants include sulfur dioxide (SO2), nitrogen dioxide (NO2) and hydrocarbon vapors such as, for example, diesel fuel, jet fuel, gasoline, and the like. Contaminants have the potential to degrade the performance of the filtration media located within the filter. Contaminant levels may increase depending on the environment, for example, areas where fuel is being transported or on the battlefield.
CP filters are designed so that during a chemical threat—for example, an attack with chemical warfare agents or toxic threat compounds—the CP filter may contact the chemically contaminated process stream with an adsorbent media specifically designed to retain the chemical threat, thereby providing breathable air to personnel. CP filters typically contain activated, impregnated carbon. One example of impregnated carbon is ASC whetlerite, which comprises activated carbon impregnated with copper, chromium and silver. When freshly prepared, filtration media may have a high capacity for the removal of chemical agents and toxic threat compounds.
ASC whetlerite comprises a high surface area of activated carbon into whose pores may be dispersed, via a process known as wet impregnation, copper, chromium and silver compounds. ASC whetlerite is prepared via a method similar to that employed in the preparation of activated, impregnated carbon.
CP filters typically operate on a continuous or near continuous basis, processing large volumes of air, for example, greater than approximately 100,000,000 (one hundred million) cubic feet of air per year of operation for an M98 particulate gas filter. Because of the large volume of air processed, over their service life, CP filters may be exposed to significant quantities of one or more of airborne contaminants and battlefield contaminants. These contaminants, while present in low quantities, may, over time, pose a significant hazard.
A filter's ability to remove one or more of chemical warfare agents and toxic chemicals may be decreased by contact with one or more of airborne contaminants and battlefield contaminants. Airborne contaminants may comprise one or more of fuel vapors, sulfur dioxide and nitrogen dioxide, for example. Battlefield contaminants may comprise one or more of fuel vapors, vapors from decontamination solvents, rocket exhaust, smoke and acid vapors, for example. Acid vapors may comprise hydrogen chloride (HCl), which may be a component of rocket exhaust. The decreased chemical protection capability resulting from exposure to one or more of airborne contaminants and battlefield contaminants may be attributed to interactions with the filtration material. Airborne contaminants and battlefield contaminants may degrade filtration performance by, for example, performing one or more of physically blocking pores of the granule, degrading the pore structure, and interacting with impregnants.
Sulfur dioxide and nitrogen dioxide are not only present at low ambient concentrations throughout the world, especially in urban areas, but may be predominant in areas where fuel is burned due to combustion. Once the CP filtration media comes into contact with air comprising one or more of sulfur dioxide and nitrogen dioxide, the filtration media's effective life against other toxic chemicals, such as cyanogen chloride and hydrogen cyanide, may be reduced. Sulfur dioxide will be oxidized within the pores of the carbon granule, leading to the formation of sulfur trioxide (SO3). Sulfur trioxide will subsequently react with one or more base metal impregnants, for example, copper. Such a reaction with copper may lead to the formation of copper sulfate (CuSO4). Copper sulfate may be relatively ineffective in its ability to react with acid gases, for example, hydrogen cyanide.
Nitrogen dioxide may react with the surface of the carbon, forming surface oxygen and liberating nitrogen oxide (NO). Interactions with nitrogen oxide may lead to an acidic carbon surface and degradation in the pore structure. One or more of the acidic surface and the degradation in the pore structure may reduce the ability of activated, impregnated carbon to remove one or more of chemical warfare agents and toxic chemicals. Fuel vapors, while not interacting with the base metal impregnants or the surface of carbon, degrade the performance of the CP filter by physically blocking the pores of activated, impregnated carbon. This physical blocking may prevent access of one or more of chemical warfare agents and toxic chemicals to reactive impregnants that may be located within the pores of the carbon granule. As a result of prolonged exposure to the environment, the media in the collective protection filter becomes contaminated. The contamination may reach a point where the filter may no longer be able to provide a minimum level of chemical protection.
Therefore, according to embodiments of the invention, the Guard Bed comprises one or more media with a high capacity for removal of one or more of sulfur dioxide, nitrogen dioxide, and fuel vapors. According to embodiments of the invention, one effective media for the removal of one or more of sulfur dioxide and nitrogen dioxide may be zirconium hydroxide. According to other embodiments of the invention, another effective media for the removal of one or more of sulfur dioxide and nitrogen dioxide may be zirconium hydroxide loaded with base metals. For example, according to further embodiments of the invention, the base metals may comprise one or more of copper, zinc, cobalt, and triethlyenediamine (TEDA). Microporous activated carbon, such as coconut carbon, may be an effective media for the removal of organic vapors. According to embodiments of the invention, these media, or combinations thereof, may be employed for extending the service life of a collective protection filter.
The process by which the Guard Bed is used involves installing the Guard Bed upstream of the CP filter when the CP filter is first brought into service. Based upon the environment to which the CP filter is exposed, the Guard Bed may be replaced one or more times during the service life of the CP filter.
Airborne contaminants may degrade the filtration media, and may thereby reduce the lifetime of the CP filter. For example, severe performance degradation of a CP filter has been reported after 21 months of shipboard operation. Performance degradation was attributed to sulfur dioxide contamination of the inlet portion of the filter bed, which led to the formation of metal sulfates.
In addition to CP filter performance degradation resulting from contact with airborne contaminants, performance degradation may occur as a result of natural processes such as exposure to humid air. For example, significant performance degradation of activated, impregnated carbon has been noted as a result of humid exposure.
It is desirable to operate a CP filter for as long as possible before filter change-out becomes inevitable due to performance degradation. Embodiments of the present invention provide a method and apparatus for extending the service life of a collective protection filter.
Filters such as the United States Army's M48A1 particulate gas filter provide protection to vehicles. Filters such as the U.S. Army's M98 particulate gas filter provide protection to buildings and ships. These filters are well known to one skilled in the art.
Embodiments of the invention relate to air purification in general and specifically to apparatuses and methods for extending the service life of a collective protection filter by scrubbing one or more of airborne contaminants and battlefield contaminants.
According to one set of embodiments of the invention, adding a Guard Bed for the purpose of removing one or more of airborne contaminants and battlefield contaminants may extend the service life of the CP filter by preventing contamination of the carbon media housed inside. It may be desirable to limit the pressure drop through the filter. For example, according to other embodiments of the invention, a pressure drop through the Guard Bed may be less than approximately 1.0 inches of water. According to still other embodiments of the invention, the Guard Bed may comprise a high capacity filtration media that targets the removal of one or more of airborne contaminants and battlefield contaminants, thereby helping to prevent these contaminants from contacting the carbon media housed within the CP filter.
In order to be maximally effective, the Guard Bed may be of low volume so as not to significantly increase the pressure drop through the CP filter. For example, according to embodiments of the invention, the Guard Bed may have a volume less than approximately 25% of the volume of the media in the CP filter bed.
Therefore, the Guard Bed may have a high capacity for the removal of one or more of airborne contaminants and battlefield contaminants. Reactive contaminants, for example, sulfur dioxide and nitrogen dioxide, may be removed using a high-capacity media that targets the removal of these contaminants. Fuel vapors, for example those generated by diesel fuel, may be removed using a high porosity media to retain the vapors.
According to embodiments of the invention, examples of possible media comprised in a Guard Bed include zirconium hydroxide (Zr(OH)4), a derivative of zirconium hydroxide, zirconium hydroxide impregnated with one or more base metals, zirconium hydroxide impregnated with one or more base metals and with TEDA, zirconia-mullite composition (ZMC); Cobalt-Zirconium-Zinc-triethylenediamine (Co-ZZT), Cobalt-Zirconium-Zinc-silver-triethylenediamine (Co-ZZAT); other zirconia-based media; other zirconia-based media impregnated with TEDA; activated carbon; TEDA; aluminum hydroxide; aluminum hydroxide impregnated with TEDA; iron hydroxide; and iron hydroxide impregnated with TEDA.
According to embodiments of the invention, the base metals may comprise, for example, one or more of zinc, cobalt, copper, chromium, iron, silver, molybdenum, potassium, magnesium, sodium, and nickel. These media may be highly effective in their ability to remove one or more of airborne contaminants and battlefield contaminants. These media may also be highly effective in their ability to promote reactions that facilitate the removal of one or more of chemical warfare agents and toxic chemicals. One or more of activated carbon and zeolites may have a high capacity for the removal of organic vapors, such as fuel vapors.
According to yet other embodiments of the invention, the Guard Bed may be located upstream of the CP filter. According to still further embodiments of the invention, the CP filter comprises the Guard Bed. According to further embodiments of the invention, the Guard Bed may be removable. Removability may allow for the Guard Bed to be removed following a discrete period of time and replaced with a fresh Guard Bed. According to still other embodiments of the invention, the Guard Bed may be replaceable.
According to other embodiments of the invention, the Guard Bed may facilitate contact between the process stream and the media located within the Guard Bed. According to still other embodiments of the invention, the Guard Bed may comprise a range of possible shapes and configurations. According to yet other embodiments of the invention, media employed in the Guard Bed may be contained within a packed bed. According to still further embodiments of the invention, media employed in the Guard Bed may be immobilized in webbing. According to further embodiments of the invention, the webbing may comprise low-melt fibers.
According to still further embodiments of the invention, the media for the Guard Bed may comprise zirconium hydroxide loaded with cobalt, zinc, and TEDA (Co-ZZT). According to yet other embodiments of the invention, the media may comprise between approximately 1% and 15% cobalt by weight. According to yet further embodiments of the invention, the media may comprise between approximately 2% and 5% cobalt by weight. According to still other embodiments of the invention, the media may comprise between approximately 10% and 30% zinc by weight. According to yet other embodiments of the invention, the media may comprise between approximately 15% and 25% zinc by weight. According to further embodiments of the invention, the media may comprise between approximately 1% and 10% TEDA by weight. According to other embodiments of the invention, the media may comprise between approximately 5% and 7% TEDA by weight.
According to additional embodiments of the invention, the Guard Bed may comprise high surface area carbon, for example, coconut carbon. According to other embodiments of the invention, the high surface area carbon may enhance the ability of the Guard Bed to remove high molecular weight hydrocarbons such as those present in fuel vapors.
According to further embodiments of the invention, techniques to prepare cobalt-zinc containing zirconium hydroxide may include one or more of wet impregnation and precipitation. Precipitation may involve contacting a slurry of zirconium hydroxide with a solution of one or more of cobalt salt and zinc salt. The pH of the slurry may then be adjusted to bring about precipitation of the cobalt and zinc within the pores of the zirconium hydroxide. For example, a solution of one or more of cobalt sulfate and zinc sulfate may be contacted with a slurry of zirconium hydroxide. One or more of the zinc and cobalt may be precipitated by contacting the slurry with a base for example, sodium hydroxide or potassium hydroxide, yielding one or more of the corresponding base metal hydroxides.
Following precipitation, the zirconium hydroxide containing one or more of cobalt and zinc may be filtered. The zirconium hydroxide may be washed with deionized water. The zirconium hydroxide may then be dried to less than 5% moisture by weight. The dried powder may then be blended in a vessel with the desired amount of TEDA at a temperature sufficient to bring about sublimation of TEDA into the pores of the solid. For example, the vessel may be a V-blender operated at a temperature between room temperature and approximately 100° C.
According to yet other embodiments of the invention, zirconium hydroxide may be prepared by precipitation using, for example, one or more of zirconium oxychloride, zirconium oxynitrate, and zirconium acetate. Precipitation may involve slurrying the zirconium solution in a mixer, then adding a base—for example, one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), and lithium hydroxide (LiOH). The addition of the base may precipitate the zirconium hydroxide. Alternatively, zirconium hydroxide may be obtained from commercial sources, such as MEL Chemicals of Flemington, N.J.
In an additional set of embodiments of the invention, a method and apparatus are provided that combine a Guard Bed with a Supplemental Bed as disclosed in “METHOD AND APPARATUS FOR PROLONGING THE SERVICE LIFE OF A COLLECTIVE PROTECTION FILTER USING A SUPPLEMENTAL BED,” by Peterson, et al., co-filed herewith. According to embodiments of the invention, in order to extend the service life of the CP filter, the Guard Bed may be installed at the time the CP filter is first brought into service. The Guard Bed may be replaced at scheduled intervals. At the time the performance of the CP filter degrades to at or near replacement levels (as a result of contaminants that escape the Guard Bed combined with the natural decay of the media), the Guard Bed may be removed and replaced with the Supplemental Bed.
FIG. 1 is a schematic representation of a Collective Protection (CP) filter that includes a gas filter bed 120, a particulate filter 110, and a Guard Bed 130. The gas filter bed 120 is a carbon-based filter bed 120. The Guard Bed 130 protects the gas filter bed 120 by removing one or more of airborne contaminants and battlefield contaminants. In this embodiment, the Guard Bed 130 nests within the particulate filter 110, which in turn nests within the gas filter bed 120. The Guard Bed 130 is, for example, located within an annular space upstream of the particulate filter 110 and upstream of the gas filter bed 120. Air flows through the center of and exits radially through the Guard Bed 130, then through the particulate filter 110, and finally through the gas filter bed 120. It is also possible to integrate the Guard Bed 130 with the CP filter.
FIG. 2 is a flowchart of a method 200 for extending the service life of a collective protection (CP) filter using a Guard Bed. The order of the steps in the method 300 is not constrained to that shown in FIG. 2 or described in the following discussion. Several of the steps could occur in a different order without affecting the final result.
In block 210, a CP filter comprising a filter bed is provided.
In block 220, an airstream is passed through a Guard Bed configured to protect the filter bed by removing one or more of airborne contaminants and battlefield contaminants. Block 220 then terminates the process.
EXAMPLES
Example 1
Filtration Performance of Contaminated Activated, Impregnated Carbon (No Guard Bed)
This example illustrates performance degradation of a filter bed comprising activated, impregnated carbon resulting from contact with airborne contaminants. The ambient levels of sulfur dioxide are assumed to be approximately 10 parts per billion (ppb). Ambient levels of nitrogen dioxide are assumed to be approximately 20 ppb. The ambient concentration of diesel fuel in urban areas is assumed to be approximately 0.15 mg/m3.
A filter bed that was approximately 2.0 cm in depth with 12×30 mesh granules of activated, impregnated carbon was exposed to nitrogen dioxide for up to approximately four years of simulated ambient exposure at a residence time of approximately 0.21 seconds, which is consistent with the residence time encountered in a CP filter. Upon completion of the exposure, the filter bed was evaluated for its ability to remove hydrogen cyanide and cyanogen chloride.
The point in time at which the effluent concentration equals the breakthrough concentration is referred to as the “breakthrough time.” The breakthrough time is used to characterize filtration performance of media. Breakthrough times are presented in Table 1. Because cyanogen (C2N2) is generated as a byproduct, the cyanogen breakthrough time is taken as the breakthrough time from the hydrogen cyanide test. Breakthrough time is a term known by one skilled in the art to be defined as the time in which the effluent concentration of a toxic vapor exceeds a threshold level.
Table 1: Hydrogen cyanide and cyanogen chloride breakthrough times for activated, impregnated carbon following periods of simulated atmospheric exposure to nitrogen dioxide. Breakthrough times are given in minutes.







TABLE 1







Hydrogen cyanide and cyanogen chloride breakthrough 


times for activated, impregnated carbon following


periods of simulated atmospheric exposure to nitrogen 


dioxide. Breakthrough times are given in minutes.










Duration
HCN
C2N2
CICN













Fresh Media
24.3
20.4
26.4


6 months
25.3
20.7
23.4


1 year
23.4
19.1
23.9


2 years
21.2
16.6
16.8


3 years
18.8
12.3
13.7


4 years 
16.3
8.3
8.6









The results demonstrate that exposure of activated, impregnated carbon to prolonged ambient levels of nitrogen dioxide results in significant filtration performance degradation.

A filter bed that was approximately 2.0 cm in depth with 12×30 mesh activated, impregnated carbon was exposed to sulfur dioxide for up to approximately four years of simulated ambient exposure. Upon completion of the exposure, the filter bed was evaluated for its ability to remove hydrogen cyanide and cyanogen chloride. Breakthrough times are presented in Table 2. Again, because cyanogen is generated as a byproduct, the cyanogen breakthrough time is taken as the breakthrough time from the hydrogen cyanide test. Breakthrough time is a term known by one skilled in the art to be defined as the time in which the effluent concentration of a toxic vapor exceeds a threshold level.
Table 2: Hydrogen cyanide and cyanogen breakthrough times for activated, impregnated carbon following periods of simulated atmospheric exposure to sulfur dioxide. Breakthrough times are given in minutes.







TABLE 2







Hydrogen cyanide and cyanogen breakthrough


times for activated, impregnated carbon following 


periods of simulated atmospheric exposure to sulfur 


dioxide. Breakthrough times are given in minutes.










Duration
HCN
C2N2
CICN





Fresh Media
24.4
20.5
25.4


1 year
22.2
18.3
23.4


2 years
19.2
15.1
22.9


3 years


20.1


4 years 
15.9
11.1
17.6









The results demonstrate that exposure of activated, impregnated carbon to prolonged ambient levels of sulfur dioxide results in significant filtration performance degradation.

A filter bed that was approximately 2.0 cm in depth with 12×30 mesh activated, impregnated carbon was exposed to diesel vapors for up to approximately four years of simulated ambient exposure. Upon completion of the exposure, the filter bed was evaluated for its ability to remove hydrogen cyanide and cyanogen chloride. Breakthrough times are presented in Table 3. Again, because cyanogen is generated as a byproduct, the cyanogen breakthrough time is taken as the breakthrough time from the hydrogen cyanide test. Table 3: Hydrogen cyanide and cyanogen chloride breakthrough times for activated, impregnated carbon following periods of simulated atmospheric exposure to diesel vapors. Breakthrough times are given in minutes.
















Duration
HCN
C2N2
CICN





















Fresh Media
24.3
20.4
25.4



1 year
25.1
17.4
17.7



2 years
21.9
18.2
15.3



3 years
19.4
15.3
14.6



4 years 
13.2
8.2
11.7










The results demonstrate that exposure of activated, impregnated carbon to prolonged ambient levels of diesel fuel vapors result in significant filtration performance 15 degradation.

A filter bed that was approximately 2.0 cm in depth with 12×30 mesh activated, impregnated carbon was exposed to a mixture of sulfur dioxide, nitrogen dioxide, and diesel vapors for up to approximately five years of simulated ambient exposure. Upon completion of the exposure, the filter bed was evaluated for its ability to remove hydrogen cyanide and cyanogen chloride. Breakthrough times are presented in Table 4. Again, because the cyanogen is generated as a byproduct, the cyanogen breakthrough time is taken from the hydrogen cyanide challenge.
Table 4: Hydrogen cyanide and cyanogen chloride breakthrough times for activated, impregnated carbon following periods of simulated atmospheric exposure to mixtures of nitrogen dioxide, sulfur dioxide and diesel vapors. Breakthrough times are given in minutes.







TABLE 4







Hydrogen cyanide and cyanogen chloride breakthrough


times for activated, impregnated carbon following 


periods of simulated atmospheric exposure to mixtures


of nitrogen dioxide, sulfur dioxide and diesel vapors. 


Breakthrough times are given in minutes.












Duration
HCN
C2N2
CICN
















Fresh Media
24.3
20.4
25.4



1 year
21.1
15.6
18.3



2 years
17.8
10.1
11.5



3 years
13.5
4.4
7.1



4 years 
10.3
2
2.8



5 years
6.3
0.1
0.8










The results demonstrate that the exposure of a filter bed comprising activated, impregnated carbon to prolonged ambient levels of a mixture of airborne contaminants and battlefield contaminants results in significant filtration performance degradation.

Example 2
Preparation of Co-ZZT for Use with a Guard Bed
A zinc-cobalt solution is prepared for use with a Guard Bed by dissolving approximately 34 pounds of zinc oxide (ZnO) in approximately 30 gallons of deionized (DI) water while mixing the components using sulfuric acid. Once completely dissolved, approximately 28.2 pounds of cobalt sulfate was added and dissolved using mixing. The total volume of the solution was then brought to approximately 50 gallons.
To a 500-gallon vessel, approximately 120 gallons of deionized (DI) water were added. To the water approximately 200 pounds (dry basis) of zirconium hydroxide were added. During the precipitation, the temperature of the slurry was controlled at approximately 20±3° C. Using a 50% potassium hydroxide solution, the pH of the slurry was then increased to approximately 11.0. The slurry was mixed for approximately two hours prior to initiating the precipitation. Following the two hours of mixing, the precipitation of the zinc-cobalt was initiated. The precipitation was initiated by pumping the zinc-cobalt solution into the slurry at a rate of approximately 1 gallon per minute. A solution of approximately 30% potassium hydroxide was then pumped into the slurry at a rate sufficient to maintain a near-constant pH of approximately 11.0 during precipitation. Upon completion of the precipitation, the slurry was then mixed for approximately four additional hours, and then was allowed to stand overnight. The amount of cobalt and zinc added to the slurry yielded a product with a nominal composition of approximately 17 parts by weight zinc, approximately 3 parts by weight cobalt, and approximately 100 parts by weight zirconium hydroxide.
In the morning, the product was filtered, and then was reslurried with approximately 200 gallons of DI water for the purpose of washing residual potassium and sulfate from the product. The washed product was then filtered and dried in a forced convection oven to less than approximately 5% moisture at a temperature of approximately 80° C.
Approximately 85 pounds of dried cobalt-zinc-zirconium hydroxide powder was then added to a V-blender, along with the target mass of TEDA necessary to achieve a loading of approximately 6%. While mixing, the V-blender was sealed and heated to approximately 60° C. To complete the TEDA sublimation, the temperature was maintained for approximately five hours. Following the approximately five hours of mixing, the V-blender and contents were allowed to cool to room temperature while mixing.
Upon completion of the TEDA sublimation operation, the powder was forwarded for particle formation. Particle formation was performed by adding the powder (referred to as Co-ZZT) to the roll compactor in order to make briquettes. The powder is referred to as Co-ZZT based on its components of cobalt (Co), zirconium hydroxide (Z), zinc (Z), and TEDA. The briquettes were then ground using a hammer mill. The product was sieved to generate 20×40 mesh granules. The density of the 20×40 mesh granules was approximately 1.2 g/cm3.
Example 3
Formation of Zirconium Hydroxide Particles
Zirconium hydroxide particle formation was performed for use with a Guard Bed. Particles were formed by adding zirconium hydroxide powder to a roll compactor in order to form briquettes. The briquettes were then ground using a hammer mill. The product was sieved to generate 20×40 mesh granules. The density of the 20×40 mesh granules was approximately 1.1 g/cm3.
Example 4
Removal of Airborne Contaminants Using Zirconium-Based Media with a Guard Bed
This example illustrates the high capacity of a Guard Bed comprising zirconium hydroxide and Co-ZZT media to remove one or more of the airborne and battlefield contaminants sulfur dioxide, nitrogen dioxide, and hydrogen chloride. 20×40 mesh granules of media were added to a test cell with a diameter of approximately 4.1 cm so as to achieve a depth of approximately 1.0 cm. The filter bed was challenged with 2,000 mg/m3 of sulfur dioxide in air at a relative humidity (RH) of approximately 15% and a temperature of approximately 25° C. The flow rate through the filter bed was approximately 5.2 liters/min of air, referenced to 25° C. The effluent concentration of sulfur dioxide was monitored until the effluent concentration approximately equaled that of the feed. At this time, the test was terminated. Test results were used to calculate the capacity of the media to remove the target contaminant. The sulfur dioxide capacity, expressed in milligrams of sulfur dioxide retained by the media per cubic centimeter of filtration media (mg/cm3), was determined by dividing the mass of sulfur dioxide retained on the filtration media by the volume of the media comprised in the filter bed.
A similar test was performed with nitrogen dioxide at a relative humidity of approximately 80%, employing a challenge concentration of approximately 1,000 gm/m3. A similar test was performed at 15% relative humidity with hydrogen chloride, employing a challenge concentration of approximately 4,000 mg/m3. Table 5 reports the filtration capacity for zirconium hydroxide (from Example 3) and Co-ZZT (from Example 2). Data corresponding to activated, impregnated carbon are shown for comparison.
Table 5. Capacity of filtration media to remove airborne contaminants.







TABLE 5







Capacity of filtration media to remove airborne contaminants.













Impregnated 


Acid Gas
Zr(OH)4
Co-ZZT
Carbon





HCl
105 mg/cm3
180 mg/cm3
 70 mg/cm3


SO2
 90 mg/cm3
120 mg/cm3
 40 mg/cm3


NO2
N/A
150 mg/cm3
>100 mg/cm3









The results demonstrate that both zirconium hydroxide and Co-ZZT have a significantly greater capacity than impregnated, activated carbon alone for the removal of one or more of airborne contaminants and battlefield contaminants known to degrade filtration performance.
Example 5
Airborne Contaminant Removal Capability of Guard Bed
A Guard Bed comprising an approximately 0.45 cm deep inlet layer of 20×40 mesh Co-ZZT and an approximately 0.2 cm deep outlet layer of 12×30 mesh coconut shell carbon was challenged as described in Example 1 employing a linear velocity of approximately 40 cm/s with ambient levels of nitrogen dioxide and sulfur dioxide for simulated periods of exposure of up to approximately four years. During this time, the effluent concentrations of nitrogen dioxide and sulfur dioxide were monitored so that the percentage of each contaminant removed could be determined. Table 6 reports the percentage of sulfur dioxide and nitrogen dioxide removed by the Guard Bed following discrete periods of simulated exposures.
Table 6: Percentage of sulfur dioxide and nitrogen dioxide removed by the Guard Bed as a function of the simulated exposure duration.







TABLE 6







Percentage of sulfur dioxide and nitrogen dioxide removed


by the Guard Bed as a function of the simulated exposure duration.










% SO2
% NO2


Duration
Removed
Removed





6 months
97.7%
61.2%


1 year
92.7%
45.1%


2 years
76.8%
30.3%


3 years
62.1%
22.4%


4 years 
51.8%
18.0%









The results demonstrate that the Guard Bed is able to remove significant levels of sulfur dioxide and moderate levels of nitrogen dioxide over approximately four years of ambient exposure.

A Guard Bed comprising an approximately 0.45 cm deep inlet layer of 20×40 mesh Co-ZZT and an approximately 0.2 cm deep outlet layer of 12×30 mesh coconut shell carbon was challenged as described in Example 1 with ambient levels of nitrogen dioxide, sulfur dioxide, and diesel vapors for simulated periods of exposure of up to approximately four years. During this time, the effluent concentrations of nitrogen dioxide, sulfur dioxide and diesel vapors were monitored so that the percentage of each contaminant removed could be determined. Table 7 reports the percentage of nitrogen dioxide, sulfur dioxide and diesel vapors removed by the Guard Bed following discrete periods of simulated exposures.
Table 7: Percentage of sulfur dioxide, nitrogen dioxide and diesel vapors removed by the Guard Bed as a function of the simulated exposure duration.







TABLE 7







Percentage of sulfur dioxide, nitrogen dioxide and 


diesel vapors removed by the Guard Bed as a 


function of the simulated exposure duration.











% SO2
% NO2
Diesel


Duration
Removed
Removed
Removed





6 months
98.2%
64.1%
75.9%


1 year
94.8%
44.8%
50.8%


2 years
83.2%
29.1%
44.4%


3 years
72.2%
22.2%
33.1%


4 years 
63.1%
20.0%
26.0%









The results demonstrate that the Guard Bed is able to remove significant levels of sulfur dioxide and moderate levels of diesel vapors and moderate levels of nitrogen dioxide over approximately four years of ambient exposure.

A Guard Bed comprising an approximately 0.25 cm deep inlet layer of 20×40 mesh Co-ZZT and an approximately 0.5 cm deep outlet layer of 12×30 mesh coconut shell carbon was challenged as described in Example 1 with ambient levels of nitrogen dioxide and sulfur dioxide for simulated periods of exposure of up to approximately four years. During this time, the effluent concentrations of nitrogen dioxide, sulfur dioxide and diesel vapors were monitored so that the percentage of each contaminant removed could be determined. Table 8 reports the percentage of nitrogen dioxide, sulfur dioxide and diesel vapors removed by the Guard Bed following discrete periods of simulated exposures.
Table 8: Percentage of sulfur dioxide, nitrogen dioxide and diesel vapors removed by the above Guard Bed as a function of the simulated exposure duration.







TABLE 8







Percentage of sulfur dioxide, nitrogen dioxide and 


diesel vapors removed by the above Guard Bed as a 


function of the simulated exposure duration.













% SO2
% NO2
Diesel



Duration
Removed
Removed
Removed







6 months
95.5%
73.9%
93.9%



1 year
85.4%
57.3%
78.2%



2 years
65.4%
39.1%
55.7%



3 years
55.0%
30.7%
42.0%



4 years 
48.0%
25.4%
35.3%










The results demonstrate that the Guard Bed is able to remove significant levels of sulfur dioxide and moderate levels of diesel vapors and moderate levels of nitrogen dioxide over approximately four years of ambient exposure.

As the above examples demonstrate, the Guard Bed is able to remove a significant fraction of the airborne contaminants, and is thus expected to extend the service life of the CP filter.
While the above representative embodiments have been described with certain components in exemplary configurations, it will be understood by one of ordinary skill in the art that other representative embodiments can be implemented using different configurations and/or different components.
Alternative embodiments of the invention may utilize systems different from the system depicted in FIGS. 1 and 2.
Alternative embodiments of the invention may comprise alternative media. Other alternative embodiments of the invention may comprise alliterative locations of the Guard Bed. Still other alliterative embodiments of the invention may comprise use of more than one Guard Bed.
The representative embodiments and disclosed subject matter, which have been described in detail herein, have been presented by way of example and illustration and not by way of limitation. It will be understood by those skilled in the art that various changes may be made in the form and details of the described embodiments resulting in equivalent embodiments that remain within the scope of the appended claims.

## Claims

1. A method for extending the service life of a collective protection (CP) filter, the method comprising:
providing at least one CP filter comprising a filter bed; and
passing an airstream through a guard bed configured so as to protect the filter bed by removing one or more airborne contaminants from the airstream prior to the CP filter bed,
wherein the guard bed comprises one or more of zirconium hydroxide (Zr(OH)4), a derivative of zirconium hydroxide, zirconium hydroxide impregnated with one or more base metals, zirconium hydroxide impregnated with one or more base metals and with triethylenediamine (TEDA), cobalt-zirconium-zinc-triethylenediamine (Co-ZZT), cobalt-zirconium-zinc-silver-triethylenediamine (Co-ZZAT), other zirconia-based media, other zirconia-based media impregnated with TEDA, activated carbon, coconut shell carbon, aluminum hydroxide, and aluminum hydroxide impregnated with TEDA.

2. The method of claim 1, wherein the airborne contaminants comprise one or more of sulfur dioxide, nitrogen dioxide, hydrocarbon vapors, fuel vapors, acid vapors, and HCl vapors.

3. The method of claim 1, wherein the base metals comprise one or more of zinc, cobalt, copper, chromium, iron, silver, molybdenum, potassium, magnesium, sodium, and nickel.

4. The method of claim 1, wherein the guard bed comprises at least one media that is immobilized in webbing.

5. The method of claim 1, wherein the guard bed is located upstream of the filter bed.

6. The method of claim 1, wherein the guard bed is incorporated with or integral to the CP filter.

7. The method of claim 1, wherein the guard bed is replaceable.

8. The method of claim 1, wherein the guard bed has a volume less than approximately 25% of the volume of the media in the filter bed.

9. The method of claim 1, wherein a pressure drop through the guard bed is less than approximately 1.0 inches of water.

10. The method of claim 1, wherein the guard bed comprises Cobalt-Zirconium-Zinc-triethylenediamine (TEDA) (Co-ZZT).

11. The method of claim 10, wherein the guard bed comprises between approximately 1% and approximately 15% cobalt by weight.

12. The method of claim 10, wherein the guard bed comprises between approximately 2% and approximately 5% cobalt by weight.

13. The method of claim 10, wherein the guard bed comprises between approximately 10% and approximately 30% zinc by weight.

14. The method of claim 10, wherein the guard bed comprises between approximately 15% and approximately 25% zinc by weight.

15. The method of claim 10, wherein the guard bed comprises between approximately 1% and approximately 10% TEDA by weight.

16. The method of claim 10, wherein the guard bed comprises between approximately 5% and approximately 7% TEDA by weight.

17. An apparatus for extending the service life of a Collective Protection (CP) filter, the apparatus comprising:
a CP filter comprising a filter bed; and
a guard bed configured so as to protect the filter bed by removing one or more of airborne contaminants from an airstream prior to the CP filter bed;
wherein the guard bed comprises one or more of zirconium hydroxide (Zr(OH)4), a derivative of zirconium hydroxide, zirconium hydroxide impregnated with one or more base metals, zirconium hydroxide impregnated with one or more base metals and with triethylenediamine (TEDA), cobalt-zirconium-zinc-triethylenediamine (Co-ZZT), cobalt-zirconium-zinc-silver-triethylenediamine (Co-ZZAT), other zirconia-based media, other a zirconia-based media impregnated with TEDA, activated carbon, coconut shell carbon, aluminum hydroxide, and aluminum hydroxide impregnated with TEDA.

18. The apparatus of claim 17, wherein the airborne contaminants comprise one or more of sulfur dioxide, nitrogen dioxide, hydrocarbon vapors, and fuel vapors, acid vapors and HCl vapors.

19. The apparatus of claim 17, wherein the base metals comprise one or more of zinc, cobalt, copper, chromium, iron, silver, molybdenum, potassium, magnesium, sodium, and nickel.

20. The apparatus of claim 17, wherein the guard bed comprises at least one media that is immobilized in webbing.

21. The apparatus of claim 17, wherein the guard bed is located upstream of the filter bed.

22. The apparatus of claim 17, wherein the guard bed is incorporated with or integral to the CP filter.

23. The apparatus of claim 17, wherein the guard bed is replaceable.

24. The apparatus of claim 17, wherein the guard bed has a volume less than approximately 25% of the volume of the media in the filter bed.

25. The apparatus of claim 17, wherein a pressure drop through the guard bed is less than approximately 1.0 inches of water.

26. The apparatus of claim 17, wherein the guard bed comprises Cobalt-Zirconium-Zinc-triethylenediamine (TEDA) (Co-ZZT).

27. The apparatus of claim 26, wherein the guard bed comprises between approximately 1% and approximately 15% cobalt by weight.

28. The apparatus of claim 26, wherein the guard bed comprises between approximately 2% and approximately 5% cobalt by weight.

29. The apparatus of claim 26, wherein the guard bed comprises between approximately 10% and approximately 30% zinc by weight.

30. The apparatus of claim 26, wherein the guard bed comprises between approximately 15% and approximately 25% zinc by weight.

31. The apparatus of claim 26, wherein the guard bed comprises between approximately 1% and approximately 10% TEDA by weight.

32. The apparatus of claim 26, wherein the guard bed comprises between approximately 5% and approximately 7% TEDA by weight.